Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
  • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G6/00—Condensation polymers of aldehydes or ketones only
  • C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/02—Condensation polymers of aldehydes or ketones only
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to radiation-curable resins based on ketone-aldehyde and to urea-aldehyde resins and to a process for preparing them.
• Radiation-curable coating materials have increasingly gained importance within recent years, due to, for example, the low VOC (volatile organic compounds) content of these systems.
• the film-forming components in the coating material are of relatively low molecular mass and hence of low viscosity, so that there is no need for high fractions of organic solvents.
• Durable coatings are obtained by the formation, following application of the coating material, of a high molecular mass, polymeric network by means of crosslinking reactions initiated, for example, by UV light.
• Ketone-aldehyde resins are used in coating materials, for example, as additive resins in order to enhance certain properties such as initial drying rate, gloss, hardness or scratch resistance. Due to their relatively low molecular weight, customary ketone-aldehyde resins possess a low melt viscosity and solution viscosity and therefore also serve as film-forming functional fillers in coating materials.
• Ketone-aldehyde resins normally possess hydroxyl groups and can therefore be crosslinked only with, for example, polyisocyanates or amine resins. These crosslinking reactions are usually initiated and/or accelerated thermally.
• the ketone-aldehyde resins are not suitable.
• the ketone-aldehyde resins are normally added to radiation-curable coating systems as, for example, a film-forming component, but not as a crosslinking component. Due to the uncrosslinked resin fractions, the resistance of such coatings to gasoline, chemicals or solvents, for example, is often relatively low.
• WO 95/17476, DE 23 45 624, EP 736 074, DE 28 47 796, DD 24 0318, DE 24 38 724, and JP 09143396 describe the use of ketone-aldehyde resins and ketone resins, e.g., cyclohexanone-formaldehyde resins, in radiation-curable systems. Radiation-induced crosslinking reactions of these resins are not described.
• EP 0 902 065 describes the use of nonradiation-curable resins formed from urea (derivatives), ketone or aldehydes as an added component in a mixture with radiation-curable resins.
• the first embodiment of which includes a radiation-curable resin comprising:
• the present invention provides a radiation-curable resin obtained by polymer-analogously reacting
• the present invention provides a process for preparing a radiation-curable resin, comprising:
• these ketone-aldehyde resins and/or urea-aldehyde resins which possess ethylenically unsaturated moieties, in the presence of suitable compounds such as photoinitiators, and in the presence if desired of suitable photosensitizers, can, by induction with, for example, UV light, be converted into a polymeric network which depending on the fraction of ethylenically unsaturated groups possesses resistance and hardness which is high to very high.
• the present invention provides radiation-curable resins comprising
• the present invention also provides radiation-curable resins obtained by polymer-analogous reaction of
• Polymer-analogous reaction means that a polymer is further reacted either to add functional groups or to block or protect functional groups.
• ketone-aldehyde resins A) and/or urea-aldehyde resins B) can be replaced by further suitable polymers, such as hydroxy-functional polyethers, polyesters and/or polyacrylates, for example.
• suitable polymers such as hydroxy-functional polyethers, polyesters and/or polyacrylates, for example.
• mixtures of these polymers with the ketone-aldehyde resins and/or urea-aldehyde resins can directly be reacted polymer-analogously with component C).
• Suitable ketones for preparing the ketone-aldehyde resins include all ketones, especially acetone, acetophenone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals containing in total 1 to 8 carbon atoms, individually or in a mixture.
• alkyl substituted cyclohexanones include 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, and 3,3,5-trimethylcyclohexanone.
• any of the ketones said in the literature to be suitable for ketone resin syntheses can be used.
• Suitable aldehyde components of the ketone-aldehyde resins include in principle linear or branched aldehydes, such as formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valeraldehyde, and dodecanal.
• aldehydes such as formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valeraldehyde, and dodecanal.
• formaldehyde such as formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valeraldehyde, and dodecanal.
• formaldehyde alone or in mixtures.
• the requisite formaldehyde is normally used in the form of an aqueous or alcoholic (e.g. methanol or butanol) solution with a strength of from about 20 to 40% by weight.
• the strength of the solution includes all values and subvalues therebetween, especially including 22, 24, 26, 28, 30, 32, 34, 36 and 38% by weight.
• Other forms of formaldehyde such as para-formaldehyde or trioxane, for example, are likewise possible.
• Aromatic aldehydes, such as benzaldehyde can likewise be present in a mixture with formaldehyde.
• Particularly preferred starting compounds used for component A) are acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, and heptanone, alone or in a mixture, and formaldehyde.
• component B use is made of urea-aldehyde resins using a urea of the general formula (i)
• X oxygen or sulfur
• A is an alkylene radical
• n is from 0 to 3, with from 1.9 (n+1) to 2.2 (n+1) mol of an aldehyde of the general formula (ii)
• R 1 and R 2 are hydrocarbon radicals (e.g. alkyl, aryl and/or alkylaryl radicals) each having up to 20 carbon atoms and/or formaldehyde.
• Suitable aldehydes of the general formula (ii) are, for example, isobutyraldehyde, 2-methylpentanal, 2-ethylhexanal, and 2-phenylpropanal, and also mixtures thereof. Preference is given to isobutyraldehyde.
• Formaldehyde can be used in aqueous form, which may also include, in part or entirely, alcohols such as methanol or ethanol, for example, or else as paraformaldehyde and/or trioxane.
• compositions are described, in, for example, DE 27 57 220, DE A 27 57 176, and EP0271 776.
• the radiation-curable resins on which the invention is based are obtained by polymer-analogous reaction of the ketone-aldehyde resins and/or of the urea-aldehyde resins, in the melt or in a suitable solvent solution, with component C).
• Suitability is possessed by maleic anhydride, (meth)acrylic acid derivatives such as (meth)acryloyl chloride, glycidyl (meth)acrylate, (meth)acrylic acid and/or the low molecular mass alkyl esters and/or anhydrides thereof, alone or in a mixture.
• radiation-curable resins by reacting the ketone-aldehyde resins and urea-aldehyde resins with isocyanates possessing an ethylenically unsaturated moiety, such as (meth)acryloyl isocyanate, ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate, (meth)acryloylalkyl isocyanate with alkyl spacers possessing from 1 to 12, preferably from 2 to 8, more preferably from 2 to 6 carbon atoms, such as methacryloylethyl isocyanate and methacryloylbutyl isocyanate, for example.
• isocyanates possessing an ethylenically unsaturated moiety such as (meth)acryloyl isocyanate, ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate, (meth)acryloylalkyl isocyanate with alkyl spacers
• reaction products which have proven suitable are those of hydroxyalkyl(meth)acrylates whose alkyl spacers have from 1 to 12, preferably from 2 to 8, more preferably from 2 to 6 carbon atoms and diisocyanates such as, for example, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, bis(isocyanatophenyl)methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane di
• polyisocyanates are the compounds having more than two isocyanate groups per molecule which are prepared by trimerizing, allophanatizing, biuretizing and/or urethaneizing the simple diisocyanates, examples being the reaction products of these simple diisocyanates, such as IPDI, HDI and/or HMDI, for example, with polyhydric alcohols (e.g., glycerol, trimethylolpropane, pentaerythritol) and/or polyfunctional polyamines or else the triisocyanurates obtainable by trimerizing the simple diisocyanates, such as IPDI, HDI, and HMDI, for example.
• polyhydric alcohols e.g., glycerol, trimethylolpropane, pentaerythritol
• polyfunctional polyamines e.g., polyfunctional polyamines
• trimerizing the simple diisocyanates such as IPDI, HDI, and HMDI, for example.
• Suitable catalyst for preparing the resins of the invention.
• Suitable compounds are all those known in the literature which accelerate an OH—NCO reaction, such as diazabicyclooctane (DABCO) or dibutyltin dilaurate (DBTL) for example.
• DABCO diazabicyclooctane
• DBTL dibutyltin dilaurate
• the functionality of the resins obtained ranges from low to high in accordance with the ratio of the reactants to one another. Through the choice of reactants it is also possible to set the subsequent hardness of the crosslinked film. If, for example, a hard resin such as cyclohexanone-formaldehyde resin is reacted with ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate, the resulting products are harder than those obtained through the use of (meth)acryloylethyl isocyanate and/or hydroxyethyl acrylate-isophorone diisocyanate adducts; the flexibility, however, is then lower.
• a hard resin such as cyclohexanone-formaldehyde resin is reacted with ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate
• the resulting products are harder than those obtained through the use of (meth)acryloylethyl isocyanate and/or
• ketone-aldehyde resins and/or urea-aldehyde resins by further hydroxy-functionalized polymers such as hydroxy-functional polyethers, polyesters and/or polyacrylates, for example.
• hydroxy-functional polyethers such as hydroxy-functional polyethers, polyesters and/or polyacrylates
• mixtures of these polymers with the ketone-aldehyde resins and/or urea-aldehyde resins can be reacted polymer-analogously with component C).
• the further hydroxy-functional polymers generally possess number average molecular weights Mn of between 200 and 10 000 g/mol, preferably between 300 and 5 000 g/mol.
• the number average molecular weight includes all values and subvalues therebetween, especially including 300, 400, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000 and 9500 g/mol.
• the present invention also provides a process for preparing radiation-curable resins by polymer-analogously reacting
• the resins on which the invention is based are prepared in the melt or in a suitable, organic solvent solution of the ketone-aldehyde resins and/or urea-aldehyde resins.
• Said organic solvent may if desired likewise possess unsaturated moieties, in which case it acts directly as a reactive diluent in the subsequent application.
• the compound C) in the presence if desired of a suitable catalyst, is added to the solution or melt of the ketone-aldehyde resins A) and/or urea-aldehyde resins B).
• the temperature of the reaction is selected in accordance with the reactivity of component C). Where isocyanates are used as component C), suitable temperatures have been found to be between 30 and 150° C., preferably between 50 and 140° C. The temperature includes all values and subvalues therebetween, especially including 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140 and 145° C.
• the solvent that may be present can be separated off if desired after the end of the reaction, in which case a powder of the product of the invention is generally obtained.
• component C 1 mol of the ketone-aldehyde resins and/or urea-aldehyde resins—based on M n number average molecular weight—with from 0.5 to 15 mol, preferably from 1 to 10 mol, in particular from 2 to 8 mol of the unsaturated compound (component C).
• the amount of component C) includes all values and subvalues therebetween, especially including 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 9, 10, 11, 12, 13 and 14 mol.
• the compound C) in the presence if desired of a suitable catalyst, is added to the solution or melt of the ketone-aldehyde resins A) and/or urea-aldehyde resins B) and the hydroxy-functional polymer, such as polyether, polyester and/or polyacrylate, for example.
• the temperature of the reaction is selected in accordance with the reactivity of component C). Where isocyanates are used as component C), suitable temperatures have been found to be between 30 and 150° C., preferably between 50 and 140° C. The temperature includes all values and subvalues therebetween, especially including 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140 and 145° C.
• the solvent that may be present can be separated off if desired after the end of the reaction, in which case a powder of the product of the invention is generally obtained.
• component C 1 mol of the ketone-aldehyde resins and/or urea-aldehyde resins and/or additional polymers—based on M n —with from 0.5 to 15 mol, preferably from 1 to 10 mol, in particular from 2 to 8 mol of the unsaturated compound (component C).
• the amount of component C) includes all values and subvalues therebetween, especially including 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 9, 10, 11, 12, 13 and 14 mol.
• a di- and trifunctional isocyanate is added to the solution or melt of the ketone-aldehyde resins A) and/or urea-aldehyde resins B) and the hydroxy-functional polymer, such as polyether, polyester and/or polyacrylate, for example and a hydroxy-functional preadduct is prepared. Only then is the compound C), in the presence if desired of a suitable catalyst, added.
• the temperature of the reaction is selected in accordance with the reactivity of component C). Where isocyanates are used as component C), suitable temperatures have been found to be between 30 and 150° C., preferably between 50 and 140° C. The temperature includes all values and subvalues therebetween, especially including 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140 and 145° C.
• the solvent that may be present can be separated off if desired after the end of the reaction, in which case a powder of the product of the invention is generally obtained.
• component C 1 mol of the ketone-aldehyde resins and/or urea-aldehyde resins and/or additional polymers—based on M n —with from 0.5 to 15 mol, preferably from 1 to 10 mol, in particular from 2 to 8 mol of the unsaturated compound (component C).
• the amount of component C) includes all values and subvalues therebetween, especially including 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 9, 10, 11, 12, 13 and 14 mol.
• these resins can be converted by irradiation into polymeric, insoluble networks which, depending on the level of ethylenically unsaturated groups present, produce elastomers to thermosets.
• German patent application 10338562.2 filed Aug. 22, 2003 is incorporated herein by reference.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Polyurethanes Or Polyureas (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

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Citations (28)

• 2003
  • 2003-08-22 DE DE10338562A patent/DE10338562A1/de not_active Withdrawn
• 2004
  • 2004-07-02 SI SI200430273T patent/SI1508581T1/sl unknown
  • 2004-07-02 EP EP04103128A patent/EP1508581B1/de not_active Expired - Lifetime
  • 2004-07-02 PT PT04103128T patent/PT1508581E/pt unknown
  • 2004-07-02 DK DK04103128T patent/DK1508581T3/da active
  • 2004-07-02 DE DE502004003376T patent/DE502004003376D1/de not_active Expired - Lifetime
  • 2004-07-02 AT AT04103128T patent/ATE358689T1/de not_active IP Right Cessation
  • 2004-07-02 ES ES04103128T patent/ES2282798T3/es not_active Expired - Lifetime
  • 2004-08-16 TW TW093124554A patent/TW200512223A/zh unknown
  • 2004-08-18 BR BR0403302-7A patent/BRPI0403302A/pt not_active IP Right Cessation
  • 2004-08-20 CN CNB2004100578728A patent/CN1322055C/zh not_active Expired - Fee Related
  • 2004-08-20 NO NO20043468A patent/NO20043468L/no not_active Application Discontinuation
  • 2004-08-20 US US10/921,989 patent/US7329710B2/en not_active Expired - Fee Related
  • 2004-08-20 CA CA002478337A patent/CA2478337A1/en not_active Abandoned
  • 2004-08-20 AU AU2004205157A patent/AU2004205157A1/en not_active Abandoned

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